Peer coaching groups (PCGs) are widely implemented in the workplace. However, few empirical studies have explored the purported antecedents and outcomes from case studies and qualitative research. Additionally, extant studies on PCGs give little regard to controls or comparative groups when assessing the efficacies of PCGs. This study is the first to investigate the effects of antecedent group characteristics on outcomes in PCGs compared to Administrative Groups (ADMGs). Results indicate PCG members experience a greater sense of belonging and quality of relations than do members in ADMGs. The continuity of relationships beyond regular meetings is more important in PCGs, positively influencing the quality of relationships (QR) and sense of belonging in the groups. QR also mediates the effect on the sense of well-being in PCGs. Additionally, for both PCGs and ADMGs, Group Emotional Intelligence (GEI) boosted participants’ quality of relations, sense of belonging, and individual development, with the effect being stronger in PCGs for the latter. At the same time, a sense of belonging in ADMGs mediated GEI's impact on engagement at work. The findings show that adding PCGs to an organization’s array of developmental activities can enhance many factors affecting employee engagement, motivation, and well-being.